Hair grooming preparation

ABSTRACT

A hair treatment agent composition characteristically comprising a specific hydrophobically modified polyether urethane and cationic surfactant.  
     The hair treatment agent composition of the present invention provides has good temperature stability in terms of the viscosity, exhibits superior fluid flow characteristics, achieves smoothness and ease of arranging the hair after drying, and gives a superior sensation during use.  
     A cleaning agent composition characteristically comprising a specific hydrophobically modified polyether urethane and anionic surfactant and/or ampholytic surfactant.  
     The cleaning agent composition of the present invention has superior viscosity and is superior in terms of foam formation as well as foam durability and feels refreshing without a slimy sensation after rinsing-off.

TECHNICAL FIELD

[0001] The present invention relates to a hair treatment agentcomposition. More particularly, it relates to a hair treatment agentcomposition which has superior temperature stability of the viscosityand superior sensation during use; it relates especially to a hairconditioning agent.

[0002] The present invention relates to a cleaning agent composition.More particularly, the present invention relates to a cleaning agentcomposition that has superior viscosity and is superior in foamformation and foam durability, and feels refreshing without a slimysensation after rinsing-off.

BACKGROUND ART

[0003] Hair treatment agent compositions having so-called conditioningeffects which endow hair with smoothness and gloss and make combingeasier are commonly sold in the markets under names such as “hairrinse”, “hair treatment”, “hair conditioner”, and “hair pack”.

[0004] A quartenary ammonium salt is blended in many of these hairtreatment agent compositions as a main ingredient; it is adsorbed ontohair to give the aforementioned conditioning effects, which is apublicly known fact.

[0005] A practice of blending in a higher alcohol to form a gel-likecomplex with the quarternary ammonium salt and even adding liquid oils,waxes, silicone compounds, and natural and synthetic polymers asnecessary is also publicly known.

[0006] However, when conventional hair treatment agent compositions areused, while smoothness and such can be given to the hair without causingstickiness at the time of application and during rinsing, satisfactorysmoothness and ease of arranging the hair are hard to come by at thetime of towel drying after rinsing, during hair drying, and afterdrying.

[0007] Also, since many of the aforementioned hair conditioning agentsuse a complex of a quarternary ammonium salt and a higher alcohol forthe conditioning ingredient, the viscosity of the prepared product isdetermined by the contents and blend ratios of these, which puts manyrestrictions on recipes; adjusting the viscosity to the desired levelwhile also adjusting the sensation during use is very difficult.

[0008] In addition, the aforementioned complex of the quarternaryammonium salt and the higher alcohol varies in its structure, i.e.lamella-vesicle, depending on the preparation method; this makes itdifficult to adjust the viscosity to a fixed level; not only that, thetemperature dependence of the viscosity of a hair conditioning agentcontaining such a complex is closely related to the melting point of thecomplex and, specifically, a steep reduction in the viscosity isobserved at temperatures near the melting point, which is accompanied bya steep reduction in the stability of the product.

[0009] On the other hand, if, for purposes of solving the aforementionedproblems, a thickener, such as a so-called polymer thickener commonlyused in cosmetics including carboxyvinyl polymer and xanthan gum, isblended in these hair treatment agent compositions then various troublesarise. For example, since many of these polymer thickeners are anionicpolymer electrolytes, they form a complex with the cationic surfactantcontained in the hair conditioner and cause precipitation,which is notdesirable for the stability and appearance of the product. Also, if apolymer thickener other than the anionic ones is blended in, anundesirable sensation during use occurs after rinsing-off, such assliminess, which is characteristic of polymers.

[0010] Recently, a sensitive engineering method has been adopted forevaluating product characteristics during makeup application, andvarious factors have been found to be related to consumers' taste forthe products. Particularly regarding hair conditioning agents, variousinvestigations have been conducted to improve the tactile sensationduring rinsing, after towel drying, and after drying; the aforementionednew investigation method has revealed that consumers pay significantattention to the tactile sensation when putting the product on theirhands and to the experience of applying and spreading it on their hair.In such a process, adjusting the fluid flow characteristics (rheologicalcharacteristics) of the product to the consumers' liking becomesimportant. For this purpose, a hair treatment agent composition withproper viscosity and fluid flow characteristics is desired.

[0011] In view of the aforementioned problem, the inventors conductedearnest research and discovered that a composition comprising a cationicsurfactant and hydrophobically modified polyether urethane which canassociate in a water sobluble medium to increase the viscosity of thewater soluble medium can solve the aforementioned problems and exhibitssuperior performance as a hair treatment agent composition, thuscompleting the present invention.

[0012] The object of the present invention is to provide a hairtreatment agent composition which has good temperature stability interms of viscosity, exhibits superior fluid flow characteristics,achieves smoothness and ease of arranging the hair after drying, andgives a superior sensation during use.

[0013] In the field of cleaning agents, many products are found in themarket in the form of, for example, hair shampoo, body shampoo, facewashing agents, etc. which have had their viscosity adjusted for ease ofhandling by adding a suitable thickener to a surfactant solution.

[0014] Usually, a few percent to a few tens of percent of a surfactant,mainly an anionic surfactant solution, is blended into these productsfor the purpose of adequate foaming and stain removal; in order tothicken a highly concentrated anionic surfactant solution, typically anampholytic surfactant, cationic surfactant, and/or lipophilic nonionicsurfactant, and/or the addition of a salt such as sodium chloride iscombined in to promote micelle growth and thicken the system.

[0015] However, some anionic surfactants, such as N-acylmethyl taurate,N-acyl taurate, N-acyl isethionate, fatty acid soaps, and amino acidtype surfactants, do not grow micelles easily even with addition of theaforementioned additives; as a result, giving sufficiently satisfactoryviscosity to the product is difficult.

[0016] When the desired viscosity cannot be obtained, problems such asdripping occur during use; not only that, the feel during the use of theproduct, which recent consumers regard as very important, includingsensory characteristics such as a rich sensation from adequate viscosityand ease of spreading, is difficult to satisfy, and therefore it is verydifficult to receive high appreciation in the market.

[0017] On the other hand, if a thickener, such as a so-called polymerthickener commonly used in cosmetics including carboxyvinyl polymer andxanthan gum, is blended in these cleaning agent compositions thenvarious troubles arise. For example, when these polymer thickeners areblended in, foaming, which is regarded as the most importantcharacteristic of a cleaning agent, is hindered; furthermore, the foamonce formed becomes easy to break, resulting in problems in thedurability of foam and such. Also, if a polymer thickener is used, anundesirable sensation during use occurs after rinsing-off, such assliminess, which is characteristic of polymers. Furthermore, in a highlyconcentrated surfactant solution, the surfactant acts as a kind of saltand the solubility of the polymer is reduced due to salting out. In suchcases, not only is the polymer thickener's effect not exhibited but alsothe product has a fatal problem such as precipitation of the thickenerover time.

[0018] In view of the aforementioned problem, the inventors conductedearnest research to discover that a composition comprising an anionicsurfactant or ampholytic surfactant and hydrophobically modifiedpolyether urethane which can associate in a water sobluble medium toincrease the viscosity of the water soluble medium can solve theaforementioned problems and exhibits superior performance as a cleaningagent, thus completing the present invention.

[0019] The object of the present invention is to provide a cleaningagent composition that has superior viscosity and is superior in foamformation and foam durability, and feels refreshing without a slimysensation after rinsing-off.

DISCLOSURE OF INVENTION

[0020] That is, the present invention provides a hair treatment agentcharacteristically comprising the following ingredients (A) and (B):

[0021] (A) Hydrophobically modified polyether urethane represented bythe following general formula (1):

R¹—{(O—R²)_(k)—OCONH—R³[—NHCOO—(R⁴—O)_(n)—R⁵]_(h)}_(m)  (1)

[0022] [In this formula, R¹, R², and R⁴ denote hydrocarbon groups whichcan be identical or different from each other; R³ denotes a hydrocarbongroup that can have a urethane bond; R⁵ denotes a straight chain,branched chain, or secondary hydrocarbon group (having 24 or more,preferably 24, carbon atoms); m is the number 2 or greater; h is thenumber 1 or greater; and k and n are independent numbers in the range of0-1,000.]

[0023] (B) Cationic surfactant

[0024] Also, the present invention provides the aforementioned hairtreatment agent composition wherein R² and/or R⁴ in general formula (1)for the hydrophobically modified polyether urethane are alkylene groupshaving 2-4 carbon atoms or phenylethylene groups that can be identicalor different from each other.

[0025] Furthermore, the present invention provides the aforementionedhair treatment agent composition wherein R³ in general formula (1) forthe hydrophobically modified polyether urethane is a polyisocyanateresidue represented by R³—(NCO)_(h+1).

[0026] Also, the present invention provides said cleaning agentcomposition wherein said polyisocyanate residue represented byR³—(NCO)_(h+1)a polyisocyanate residue obtained by a reaction betweendi- to octa- hydric polyol and di- to tetra-hydric polyisocyanate.

[0027] Furthermore, the present invention provides the aforementionedhair treatment agent composition wherein R¹ in general formula (1) forthe hydrophobically modified polyether urethane is a polyol representedby R¹—(OH)_(m).

[0028] Furthermore, the present invention provides the aforementionedhair treatment agent composition wherein R⁵ in general formula (1) forthe hydrophobically modified polyether urethane is a hydrocarbon groupderived from decyltetradecyl alcohol.

[0029] Furthermore, the present invention provides the aforementionedhair treatment agent composition wherein the hydrophobically modifiedpolyether urethane represented by general formula (1) is a product of areaction between one, two or more polyether polyols represented byR¹—[(O—R²)_(k)—OH]_(m), one, two or more polyisocyanates represented byR³—(NCO)_(h+1), and one, two or more polyether monoalcohols representedby HO—(R⁴—O)_(n)—R⁵.

[0030] Furthermore, the present invention provides the aforementionedhair treatment agent composition wherein the cationic surfactant is aquartenary ammonium salt represented by the following general formula(2) or an amidoamine type compound represented by the following generalformula (3).

[0031] [In this formula, R3 denotes an alkyl group or hydroxyalkyl grouphaving 14-22 carbon atoms, R4 denotes a benzyl group, hydroxyalkylgroup, or alkyl group having 1-3 carbon atoms, R5 and R6 denote alkylgroups or hydroxyalkyl groups independently represented by either R3 orR4, and X denotes a halogen atom or an alkylsulfuric group having 1-2carbon atoms.]

R7CONH—(CH₂)×N(R8)₂  (3)

[0032] [In this formula, R7CO— denotes a higher fatty acid residuehaving 12-24 carbon atoms, R8 denotes an alkyl group having 1-4 carbonatoms, and x is an integer 2-4.]

[0033] Also, the present invention provides the aforementioned hairtreatment agent composition wherein said quartenary ammonium salt isone, two or more selected from a group consisting of stearyltrimethylammonium chloride, cetyltrimethyl ammonium chloride, andbehenyltrimethyl ammonium chloride.

[0034] Furthermore, the present invention provides the aforementionedhair treatment composition wherein said amidoamine-type compound is one,two or more selected from a group consisting of stearamidoethyldiethylamine, stearamidopropyl dimethylamine, and behenamidopropyldimethylamine.

[0035] Also, the present invention provides the aforementioned hairtreatment composition which additionally comprises a higher alcoholand/or higher fatty acid.

[0036] Furthermore, the present invention provides the aforementionedhair treatment agent composition wherein said higher alcohol is one, twoor more selected from a group consisting of cetyl alcohol, stearylalcohol, and behenyl alcohol.

[0037] Also, the present invention provides the aforementioned hairtreatment agent composition, wherein said higher fatty acid is one, twoor more selected from a group consisting of stearic acid, palmitic acid,myristic acid, oleic acid, isostearic acid, 12-hydroxystearic acid, orbehenic acid.

[0038] Furthermore, the present invention provides the aforementionedhair treatment agent composition wherein the molar ratio of the cationsurfactant and the higher alcohol and/or higher fatty acid is 1:2-1: 10.

[0039] Also, the present invention provides the aforementioned hairtreatment agent composition wherein the blend ratio of thehydrophobically modified polyether urethane of general formula (1) is 0.1-10 wt % of the total amount of the hair treatment agent composition.

[0040] Also, the present invention provides the aforementioned hairtreatment agent composition wherein the blend ratio of a cationicsurfactant is 0.01-10 wt % of the total amount of the hair treatmentagent composition.

[0041] Furthermore, the present invention provides the aforementionedhair treatment agent composition wherein the viscosity of the hairtreatment agent composition is 1-10 Pa·s when measured at 25° C. and1s⁻¹ and/or 0.1-1 Pa·s when measured at 25° C. and 100s⁻¹.

[0042] Furthermore, the present invention provides the aforementionedhair treatment agent composition wherein said hair treatment agentcomposition is a hair conditioning agent.

[0043] Furthermore, the present invention provides the aforementionedhair treatment agent composition which additionally contains organicacid (preferably tartaric acid or glutamic acid).

[0044] That is, the present invention provides a cleaning agentcharacteristically comprising the following ingredients (A) and (B):

[0045] (A) Hydrophobically modified polyether urethane represented bythe following general formula (1):

[0046] General formula (1)

R¹—{(O—R²)_(k)—OCONH—R³[—NHCOO—(R⁴—O)_(n)—R⁵]_(h)}_(m)  (1)

[0047] [In this formula, R¹, R², and R⁴ denote hydrocarbon groups whichcan be identical or different from each other; R³ denotes a hydrocarbongroup that can have a urethane bond; R⁵ denotes a straight chain,branched chain, or secondary hydrocarbon group (having 24 or more,preferably 24, carbon atoms); m is the number 2 or greater; h is thenumber 1 or greater; and k and n are independent numbers in the range of0-1,000.]

[0048] (B) Anionic surfactant and/or ampholytic surfactant

[0049] Also, the present invention provides said cleaning agentcomposition wherein R² and/or R⁴ in general formula (1) for thehydrophobically modified polyether urethane are alkylene groups having2-4 carbon atoms or phenylethylene groups that can be identical ordifferent from each other.

[0050] Furthermore, the present invention provides said cleaning agentcomposition wherein R³ in general formula (1) for the hydrophobicallymodified polyether urethane is a polyisocyanate residue represented byR³—(NCO)_(h+1).

[0051] Also, the present invention provides said cleaning agentcomposition wherein said polyisocyanate residue represented byR³—(NCO)_(h+1) is a polyisocyanate residue obtained by a reactionbetween di- to octa- hydric polyol and di- to tetra-hydricpolyisocyanate.

[0052] Furthermore, the present invention provides said cleaning agentcomposition wherein R¹ in general formula (1) for the hydrophobicallymodified polyether urethane is a polyol represented by R¹—(OH)_(m).

[0053] Furthermore, the present invention provides said cleaning agentcomposition wherein R⁵ in general formula (1) for the hydrophobicallymodified polyether urethane is a hydrocarbon group derived fromdecyltetradecyl alcohol.

[0054] Furthermore, the present invention provides said cleaning agentcomposition wherein the hydrophobically modified polyether urethanerepresented by general formula (1) is a product of a reaction betweenone, two or more polyether polyols represented byR¹—[(O—R²)_(k)—OH]_(m), one, two or more polyisocyanates represented byR³—(NCO)_(h+1), and one, two or more polyether monoalcohols representedby HO—(R⁴—O)_(n)—R⁵.

[0055] Also, the present invention provides said cleaning agentcomposition wherein the anionic surfactant is represented by thefollowing general formulas (4), (5), or (6).

[0056] General formula (4)

R1CO—a—(CH₂)_(n)SO₃M1  (4)

[0057] (In this formula, R1CO— denotes a saturated or unsaturated fattyacid residue having 10-22 carbon atoms on average; a denotes any of thestructures containing electron donor atoms —O—, —NH—, and/or —N(CH₃)—;M1 denotes hydrogen, alkali metal, alkaline earth metal, ammonium ororganic amine; and n denotes an integer 1-3.)

[0058] General formula (5)

R2CONH—C(b)H—COOM2  (5)

[0059] (In this formula, R2CO— denotes a saturated or unsaturated fattyacid residue having 10-22 carbon atoms on average; b denotes a hydrogenatom, —CH₃, or —(CH₂)_(n)—COOM3; M2 and M3 denote hydrogen, alkalimetal, alkaline earth metal, ammonium or organic amine; and n denotes aninteger 1-3.)

[0060] General formula (6)

R3COO—M4

[0061] (In this formula, R3COO— denotes a saturated or unsaturated fattyacid residue having 10-22 carbon atoms on average; M4 denotes hydrogen,alkali metal, alkaline earth metal, ammonium or organic amine; and ndenotes an integer 1-3.)

[0062] Furthermore, the present invention provides said cleaning agentcomposition wherein the anionic surfactant is one, two, or more chosenfrom a group consisting of N-acylmethyl taurate, N-acyl taurate, andN-acyl isethionate.

[0063] Also, the present invention provides said cleaning agentcomposition wherein the ampholytic surfactant is an acetic acid betainetype or imidazoline type ampholytic surfactant.

[0064] Furthermore, the present invention provides said cleaning agentcomposition wherein the weight ratio between the anionic surfactant andthe ampholytic surfactant is 10:0-2:8.

[0065] Also, the present invention provides said cleaning agentcomposition wherein the blend ratio of the hydrophobically modifiedpolyether urethane of general formula (1) is 0.1-10 wt % of the totalamount of the cleaning agent composition.

[0066] Furthermore, the present invention provides said cleaning agentcomposition wherein the blend ratio of the anionic surfactant or theampholytic surfactant is 5-40 wt % of the total amount of the cleaningagent composition.

[0067] Also, the present invention provides the aforementioned cleaningagent composition wherein the viscosity of the cleaning agentcomposition is 1-10 Pa·s when measured at 25° C. and 1s⁻¹ and/or 0.1-1Pa·s when measured at 25° C. and 100s⁻¹.

[0068] Furthermore, the present invention provides said cleaning agentcomposition which additionally contains cationized starch.

BEST MODE FOR CARRYING OUT THE INVENTION

[0069] The configuration of the present invention is described in detailbelow.

[0070] (A) Hydrophobically modified polyether polyurethane of generalformula (1)

[0071] The hair treatment agent composition of the present inventioncontains a specific hydrophobic polyether polyurethane. Thehydrophobically modified polyether polyurethane used in the presentinvention functions as an associative thickener and is capable ofincreasing the viscosity of a water soluble medium, and therefore isused as a viscosity adjusting agent (refer to Japanese Patent Laid-OpenNo. Hei 9-71766 bulletin, for example).

[0072] The hydrophobic polyether polyurethane represented by generalformula (1) can be obtained by, for example, reacting one, two or morepolyetherpolyols represented by R¹—[(O—R²)_(k)—OH]_(m), one, two or morepolyisocyanates represented by R³—(NCO)_(h+1), and one, two or morepolymonoalcohols represented by HO—(R⁴—O)_(n)—R⁵. In this case R¹—R⁵ ingeneral formula (1) is determined by the R¹—[(O—R²)_(k)—OH]_(m),R³—(NCO)_(h+1), and HO—(R⁴—O)_(n)—R⁵ used. The loading ratios of thethree are not limited in particular; in terms of the ratio between thehydoxide group from the polyether polyol and the polyether monoalcoholand the isocyanate group from the polyisocyanate, NCO/OH=0.8:1-1.4:1 ispreferable.

[0073] The polyether polyol compound represented byR¹—[(O—R²)_(k)—OH]_(m) preferably used to obtain the hydrophobicallymodified polyether polyurethane of general formula (1) can be obtainedby addition polymerization of m-hydric polyol with an alkylene oxidesuch as ethylene oxide, propylene oxide, butylene oxide, orepichlorohydrin, styrene oxide, etc.

[0074] For this m-hydric polyol, di- to octa-hydric ones are preferable;examples include dihydric alcohols such as ethylene glycol, propyleneglycol, butylene glycol, hexamethylene glycol, neopentyl glycol;trihydric alcohols such as glycerin, trioxy isobutane,1,2,3-butanetriol, 1,2,3-pentatriol, 2-methyl-1 ,2,3-propanetriol,2-methyl-2 ,3,4-butanetriol, 2-ethyl-1 ,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3 ,4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, pentamethyl glycerin,pentaglycerin,1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylol ethane, andtrimethylolpropane; tetrahydric alcohols such as pentaerythritol,1,2,3,4-pentane tetrol, 2,3,4,5-hexane tetrol, 1,2,4,5-pentane tetrol,and 1,3,4, 5-hexane tetrol; pentahydric alcohols such as adonitol,arabite, and xylitol; hexahydric alcohols such as dipentaerythritol,sorbitol, mannite, and iditol; and octahydric alcohols such as sucrose.

[0075] In addition, R² is determined by the alkylene oxide, styreneoxide and such to be added; alkylene oxides or styrene oxides having 2-4carbon atoms are preferable for superior effects and easy procurement.

[0076] The alkylene oxide, styrene oxide and such to be added can beprepared by single polymerization, block polymerization or randompolymerization of two or more kinds. A conventional method can be usedfor the addition. The degree of polymerization k is 0-1,000, preferably1-500, and more preferably 10-50. When the ratio of the ethylene groupin R² is 50-100 wt % of the total R², an associative thickener suitablefor this purpose can be obtained.

[0077] The molecular weight of R¹—[(O—R²)_(k)—OH]_(m) is preferably500-100,000, and more preferably 1,000-50,000.

[0078] Selection of the polyisocyanate represented by R³—(NCO)_(h+1)which is preferably used to obtain the hydrophobically modifiedpolyether polyurethane of general formula (1) is not limited inparticular as long as it has two or more isocyanate groups in themolecule. Examples include aliphatic diisocyanate, aromaticdiisocyanate, alicycle diisocyanate, biphenyl diisocyanate, diisocyanateof phenylmethane, triisocyanate, and tetraisocyanate.

[0079] Examples of the aliphatic diisocyanate include: methylenediisocyanate, dimethylene diisocyanate, trimethylene diisocyanate,tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylenediisocyanate, dipropyl ether diisocyanate, 2,2-dimethylpentanediisocyanate, 3-methoxy hexane diisocyanate, octamethylene diisocyanate,2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxy hexane diisocyanate, 1,4-butyleneglycol dipropyl ether diisocyanate, thiodihexyl diisocyanate, metaxylylene diisocyanate, para xylylene diisocyanate, and tetramethylxylylene diisocyanate.

[0080] Examples of the aromatic diisocyanate include: meta phenylenediisocyanate, para phenylene diisocyanate, 2,4-tolylene diisocyanate,2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethyl benzenediisocyanate, isopropyl benzene diisocyanate, tolidine diisocyanate,1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate,2,6-naphthalene diisocyanate, and 2,7-naphthalene diisocyanate.

[0081] Examples of the alicycle diisocyanate include: hydrogenatedxylylene diisocyanate and isophorone diisocyanate.

[0082] Examples of the biphenyl diisocyanate include: biphenyldiisocyanate, 3,3′-dimethylbiphenyl diisocyanate, and 3,3′-dimethoxybiphenyl diisocyanate.

[0083] Examples of the diisocyanate of phenylmethane include:diphenyl-methane-4,4′-diisocyanate, 2,2′-dimethyldiphenyl-methane-4,4′-diisocyanate, diphenyldimethylmethane-4,4′-diisocyanate, 2,5,2′,5′-tetramethyldiphenyl-methane-4,4′-diisocyanate, cyclohexylbis (4-isocyanate phenyl)methane, 3,3′-dimethoxy diphenyl-methane-4,4′-diisocyanate,4,4′-dimethoxy diphenyl-methane-3,3′-diisocyanate, 4,4′-diethoxydiphenyl-methane-3,3′-diisocyanate, 2,2′-dimethyl-5,5′-dimethoxydiphenyl-methane-4,4′-diisocyanate, 3,3′-dichloro diphenyldimethylmethane-4,4′-diisocyanate, and benzophenone-3,3′-diisocyanate.

[0084] Examples of the triisocyanate include:1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, 1,3,7-naphthalene triisocyanate,biphenyl-2,4,4′-triisocyanate, diphenyl-methane-2,4,4′-triisocyanate,3-methyl diphenyl-methane-4,6,4′-triisocyanate,triphenylmethane-4,4′,4,″-triisocyanate, 1,6,11-undecane triisocyanate,1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylenetriisocyanate, bicyclo heptane triisocyanate, and tris (isocyanatephenyl) thiophosphate.

[0085] Dimers and trimers (isocyanurate bonds) of these polyisocyanatecompounds can also be used; biuret obtained by a reaction with an aminecan also be used. Furthermore, polyisocyanate having a urethane bondobtained by a reaction between these polyisocyanates and a polyol canalso be used. For the polyol, di-to octa-hydric ones are preferable; theaforementioned polyols are preferable. When tri-or-higher-hydricpolyisocyanate is used for the R³—(NCO)_(h+1), this polyisocyanatehaving a urethane bond is preferable.

[0086] Selection of the polyether monoalcohol represented byHO—(R⁴—O)_(n)—R⁵ which is preferably used to obtain the hydrophobicpolyether polyurethane of general formula (1) is not limited inparticular as long as it is a polyether of a straight chain or branchedchain secondary monohydric alcohol.

[0087] Such a compound can be obtained by addition polymerization of asecondary monohydric alcohol with an alkylene oxide such as ethyleneoxide, propylene oxide, butylene oxide, and epichlorohydrin, styreneoxide, etc.

[0088] The straight chain alcohol mentioned here is represented by thefollowing general formula (7). R⁶—OH (7)

[0089] The branched chain alcohol is represented by the followinggeneral formula (8).

[0090] The secondary alcohol is represented by the following generalformula (9).

[0091] Therefore, R⁵ is a group derived by removing a hydroxide groupfrom the aforementioned general formulas (7)-(9). In the aforementionedgeneral formulas (7)-(9), R⁶, R⁷, R⁸, R¹⁰, and R¹¹ are hydrocarbongroups.

[0092] In the aforementioned general formula (8), R⁹ is a hydrocarbongroup.

[0093] R⁵ is a hydrocarbon group having 24 or more carbon atoms,preferably an alkyl group; among them, those with a total number ofcarbon atoms of 24 are more preferable, and hydrocarbon groups derivedfrom decyltetradecyl alcohol are particularly preferable.

[0094] The present invention is based on a discovery of an unexpectedeffect of a length of the alkyl chain of R⁵ that is 24 or more carbonatoms.

[0095] That is, when a hydrophobic polyether urethane acts as anassociative thickener, the hydrophobic association is enhanced when R⁵has 24 or more carbon atoms, which in turn effectively increases theviscosity of the hair treatment agent composition containing a cationicsurfactant.

[0096] The alkylene oxide, styrene oxide and such to be added can beprepared by single polymerization, block polymerization or randompolymerization of two or more kinds. A conventional method can be usedfor the addition. The degree of polymerization k is 0-1,000, preferably1-200, and more preferably 10-50. When the ratio of the ethylene groupin R⁴ is 50-100 wt %, preferably 65-100 wt %, of the total R⁴, anassociative thickener suitable for the object of the present inventioncan be obtained.

[0097] The compound represented by the aforementioned general formula(1) can be obtained by, for example, heating at 80-90° C.for 1-3 hoursto bring the ingredients into reaction, in the same manner as in a usualreaction between polyether and isocyanate.

[0098] When the polyetherpolyols represented by R¹—[(O—R²)_(k)—OH]_(m)(a), the polyisocyanates represented by R³—(NCO)_(h+1) (b), and thepolymonoalcohol represented by HO—(R⁴—O)_(n)—R⁵ (c) are brought intoreaction, there may be byproducts other than the compound with astructure represented by general formula (1). For example, whendiisocyanate is used, the main product will be the c—b—a—b—c typecompound represented by general formula (1), but the c—b—c type, thec—b—(a—b)_(x)—a—b—c type and such may also be produced as byproducts. Insuch cases, the mixture containing the general formula (1) type compoundcan be used in the present invention without isolating the generalformula (1) type compound.

[0099] 1. A Hair treatment Agent Composition

[0100] The hair treatment agent composition of the present inventionshould preferably contain 0.1-10 wt % of the aforementionedhydrophobically modified polyether polyurethane. If the blend ratio isless than 0. 1 wt % then the effect of the addition may not be observed;if it is higher than 10 wt % then the viscosity becomes too high,causing problems in handling during preparation, sometimes resulting ina reduction in the operation efficiency, problems in extracting theproduct from the container during actual use, and/or poor spreading atthe time of application on the hair.

[0101] (B) Cationic surfactant

[0102] (B) ingredient, i.e. the cationic surfactant, is described indetail below. Selection of the cationic surfactant used in the presentinvention is not limited in particular; a quartenary ammonium saltrepresented by the aforementioned general formula (2) and an amidoaminetype compound represented by the general formula (3) are preferablyused.

[0103] Specific examples of the quartenary ammonium salt represented bygeneral formula (2) include:

[0104] cetyltrimethylammonium chloride, stearyltrimethylammoniumchloride, behenyl trimethylammonium chloride, behenyl dimethylhydroxyethyl ammonium chloride, stearyldimethylbenzylammonium chloride,and cetyltriethylammonium methylsulfate; in particular, 002; 4; 105Pages; 1 Item(s) 10049110.txt; 09/05/2002; 2; 99 Pages; 1 Item(s)10090455.txt; 09/05/2002; 3; 105 Pages; 1 Item(s) 10133780.txt;09/05/2002; 2; 98 Pages; 1 Item(s) Errors: none reported.stearyltrimethylammonium chloride, cetyltrimethylammonium chloride orbehenyltrimethylammonium chloride is preferably used.

[0105] Specific examples of the amidoamine-type compound represented bygeneral formula (3) include:

[0106] stearamidoethyl diethylamine, stearamidoethyl dimethylamine,palmitamidoethyl diethylamine, palmitamidoethyl dimethylamine,myristamidoethyl diethylamine, myristamidoethyl dimethylamine,behenamidoethyl diethylamine, behenamidoethyl dimethylamine,stearamidopropyl diethylamine, stearamidopropyl dimethylamine,palmitamidopropyl diethylamine, palmitamidopropyl dimethylamine,myristamidopropyl diethylamine, myristamidopropyl dimethylamine,behenamidopropyl diethylamine, behenamidopropyl dimethylamine; inparticular, stearamidoethyl diethylamine, stearamidopropyldimethylamine, and behenamidopropyl dimethylamine are preferably used.

[0107] The blend ratio of the cationic surfactant is preferably 0.01-10wt % of the total amount of the hair treatment agent composition. If theblend ratio is less than 0.01 wt % then smooth hair cannot be obtained.If the blend ratio is higher than 10 wt % then the solubility of thesurfactant is not sufficient and precipitation may occur due to theconcentration exceeding the saturation level; also, the conditioningeffect is no longer dependent on the concentration, making itmeaningless to add more.

[0108] In addition, the hair treatment agent composition of the presentinvention should preferably contain a higher alcohol and/or higher fattyacid.

[0109] Specific examples of the higher alcohol include: straight chainalcohols such as decanol, lauryl alcohol, cetyl alcohol, stearylalcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, andcetostearyl alcohol, as well as branched chain alcohols such asmonostearyl glycerin ether (batyl alcohol), 2-decyl tetradecyl alcohol,lanolin alcohol, cholesterol, phytosterol, hexyl dodecanol, isostearylalcohol, and octyl dodecanol; in particular, cetyl alcohol,stearylalcohol, and behenyl alcohol are preferably used.

[0110] Specific examples of the higher fatty acids include: capric acid,lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid,oleic acid, 12-hydroxystearic acid, undecylenic acid, tall oil,isostearic acid, linolic acid, linolenic acid, eicosapentaenoic acid,and docosahexaenoic acid; in particular, stearic acid, palmiticacid,myristic acid, oleic acid, isostearic acid, 12-hydroxystearic acid,and behenic acid are preferably used.

[0111] The blend ratio of the aforementioned higher alcohol and/orhigher fatty acid should preferably be such that the molar ratio of thecationic surfactant and the higher alcohol and/or higher fatty acid is1:2-1:10, more preferably 1:3-1:5.

[0112] “Viscosity”

[0113] The viscosity of the hair treatment agent composition of thepresent invention is preferably 1-10 Pa·s as measured at 25° C. and 1s⁻¹or 0.1-1 Pa·s as measured at 25° C. and 100s⁻¹. Preferably, bothconditions should be met.

[0114] For the measurement conditions of 25° C. and 1s⁻¹ (low shearrate), the aforementioned high viscosity range is preferable. If theviscosity is outside of the aforementioned range, then extracting theproduct from the container becomes difficult and spreading may becomepoor, resulting in problems during use.

[0115] For the measurement conditions of 25° C. and 100s⁻¹ (high shearrate), the aforementioned high viscosity range is preferable.

[0116] If the viscosity is outside of the aforementioned range, thendripping occurs during use when the hair treatment agent composition isput in a hand and the composition gives the impression of being thin,making it difficult to give a so-called “rich” tactile sensation.

[0117] The aforementioned viscosity can be easily achieved by thespecific hydrophobically modified polyether polyurethane of generalformula (1).

[0118] The viscosity can be measured by using a commercial cone/platetype or concentric cylinder type viscometer: for example, CSL-100 fromCarri-Med Co. Ltd.

[0119] “Other additives”

[0120] In addition to the aforementioned essential ingredients, otheringredients normally used in hair treatment agents are blended asnecessary in the hair treatment agent compositiont of the presentinvention within the range that does not affect the effect of thepresent invention; examples of such ingredients include propyleneglycol, sorbitol, humectants such as glycerin, surfactants, conditioningagents such as silicone derivatives, active agents, humectants,chelating agents, pH regulators, antiinflammatory agents, preservatives,ultraviolet absorbents, antioxidants, pigments, and perfume; andpreparation is conducted for the target formulation and application witha conventional method.

[0121] The pH of the hair treatment agent composition can be freelyadjusted by using, for example, inorganic acids such as phosphoric acid,hydrochloric acid, and sulfuric acid as well as their salts, organicacids such as citric acid, malic acid, tartaric acid, and oxalic acid,as well as their salts, inorganic bases such as sodium hydroxide,potassium hydroxide, calcium hydroxide, and ammonia as well as theirsalts, and organic bases such as triethanolamine and its salt. The pH isnot limited, but preferably adjusted to 2-7, more preferably 3-6.

[0122] We discovered that organic acid has the following unexpectedeffects on the composition of the present invention.

[0123] {circle over (1)} Reduced color loss of dyed hair

[0124] {circle over (2)} Tightening of hair cuticles and giving gloss tohair

[0125] These effects are particularly prominent when tartaric acid orglutamic acid is used for the organic acid.

[0126] The hair treatment agent composition of the present invention ispreferably used as a hair conditioning agent such as a hair rinse, hairtreatment, hair conditioner, hair pack, or conditioning shampoo.

[0127] 2. A Cleaning Agent Composition

[0128] The cleaning agent composition of the present invention shouldpreferably contain 0.1-10 wt % of the aforementioned hydrophobicallymodified polyether polyurethane. If the blend ratio is less than 0.1 wt% then the effect of the addition may not be observed; if it is higherthan 10 wt % then the viscosity becomes too high, causing problems inhandling during preparation, sometimes resulting in a reduction in thework efficiency, problems in extracting the product from the containerduring actual use, and/or poor spreading at the time of application onthe hair.

[0129] (B) Anionic surfactant and/or ampholytic surfactant

[0130] The surfactant, (B) ingredient, is described in detail below.

[0131] “Anionic surfactant”

[0132] The anionic surfactant used in the present invention is notlimited in particular; preferable examples include anionic surfactantsrepresented by the aforementioned general formulas (4), (5), and (6)Examples of (4) include cocoyl N-methyl taurate, lauryl methyl taurate,myristyl methyl taurate, sodium cocoyl taurate, and cocoyl isethionate;examples of (5) include lauroyl glutamate monosalt, lauroyl glutamatedisalt, myristoyl glutamate monosalt, myristoyl glutamate disalt,cocoacyl glutamate monosalt, cocoacyl glutamate disalt, and cocoacylglycinate; and examples of (6) include higher fatty acid salts such aslaurate, myristate, and cocoyl salt.

[0133] Examples of M1, M2, M3, and M4 in these general formulas (4),(5), and (6) include sodium, potassium, ammonium, triethanolamine, andsodium N-methyl taurate. One, two, or more of these anionic surfactantscan be used.

[0134] “Ampholytic surfactant”

[0135] Selection of the ampholytic surfactant used in the presentinvention is not limited in particular; examples include the betainetype ampholytic surfactant such as lauryl dimethylaminoacetic betaine,myristylaminoacetic betaine, and cocoylamidopropyl betaine, and theimidazoline type ampholytic surfactants such as2-cocoyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine and2-lauryl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine. One, two,or more of these ampholytic surfactants can be used.

[0136] When both of the aforementioned anionic surfactants andampholytic surfactants are used, a preferable weight ratio is 10:0-2:8.If there is more of the ampholytic surfactant than indicated by theaforementioned ratio, foam formation and foam durability becomeinferior, which is not desirable for a cleaning agent composition.

[0137] The blend ratio of the cationic surfactant is preferably 5-40 wt% of the total amount of the cleaning agent composition. If the blendratio is less than 5 wt % then foam formation is not sufficient and anadequate cleaning effect cannot be obtained. If the blend ratio ishigher than 40 wt % then the solubility of the surfactant is notsufficient and precipitation may occur due to the concentrationexceeding the saturation level; also, the cleaning effect is no longerdependent on the concentration, making it meaningless to add more.

[0138] “Viscosity”

[0139] The viscosity of the hair treatment agent composition of thepresent invention is preferably 1-10 Pa·s as measured at 25° C. and 1s⁻¹or 0.1-1 Pa·s as measured at 25° C. and 100s⁻¹.

[0140] Preferably, both conditions should be met.

[0141] For the measurement conditions of 25° C. and 1s⁻¹ (low shearrate), the aforementioned high viscosity range is preferable. If theviscosity is outside of the aforementioned range, then extracting theproduct from the container becomes difficult and spreading may becomepoor, resulting in problems during use.

[0142] For the measurement conditions of 25° C. and 100s⁻¹ (high shearrate), the aforementioned high viscosity range is preferable.

[0143] If the viscosity is outside of the aforementioned range, thendripping occurs during use when the hair treatment agent composition isput in a hand and the composition gives the impression of being thin,making it difficult to give a so-called “rich” tactile sensation.

[0144] The aforementioned viscosity can be easily achieved by thespecific hydrophobically modified polyether polyurethane of generalformula (1).

[0145] The viscosity can be measured by using a commercial cone/platetype or concentric cylinder type viscometer: for example, CSL-100 fromCarri-Med Co. Ltd.

[0146] “Other additives”

[0147] In addition to the aforementioned essential ingredients, otheringredients normally used in cleaning agents are blended as necessary inthe cleaning agent compositiont of the present invention within therange that does not affect the effect of the present invention; examplesof such ingredients include humectants such as propylene glycol,sorbitol, and glycerin, surfactants, conditioning agents such assilicone derivatives, active agents, humectants, chelating agents, pHregulators, antiinflammatory agents, preservatives, ultravioletabsorbents, antioxidants, pigments, and perfume; and preparation isconducted for the target formulation and application with a conventionalmethod.

[0148] We discovered that cationized starch has the following unexpectedeffects on the composition of the present invention.

[0149] {circle over (1)} Superior smooth sensation at the time ofrinsing

[0150] {circle over (2)} No sticky hair

[0151] For the cationized starch, a commercial product (Sensomer CI-50:Nalco) is used; the blend ratio is usually 0.01-2 wt %, preferably0.2-1.5 wt %, of the total amount of the composition.

EXAMPLES

[0152] The present invention is described in detail below by referringto Examples. The present invention is not limited to these Examples. Theblend ratio is expressed in wt % units unless specified otherwise.

[0153] Prior to Examples, preparation examples of hydrophobicallymodified polyether polyurethane are shown below.

[0154] <Preparation example A>

[0155] 550 parts of polyethylene glycol (PEG) (molecular weight 11,000)(corresponds to R¹—[(O—R²)_(k)—OH]_(m)) and 198 parts of an ethyleneoxide (EO) 20-mole adduct of a branched alcohol (corresponds toR³—(NCO)_(h+1)) represented by the following general formula (10) wereput into a 100-ml four-mouth flask equipped with a thermometer, anitrogen feed tube, and a stirrer,

[0156] and then the mixture was cooled down to 80° C., after which 29.6parts of hexamethylene diisocyanate (HMDI) (corresponds toR³—(NCO)_(h+1)) was added, followed by a two-hour reaction in a nitrogengas flow at 80-100° C.; after confirming that the isocyanate was 0%, thereaction product, consisting of light yellow solid matter at normaltemperatures, was obtained.

[0157] Various kinds of hydrophobically modified polyether polyurethanecan be prepared in a similar manner as in Preparation example A. Forexample, hydrophobically modified polyether polyurethane according toPreparation examples A-G shown in Table 1 is suitably used in thepresent invention. TABLE 1 Preparation examples A-G PreparationPreparation Preparation Preparation Preparation Preparation Preparationexample A example B example C example D example E example F example G R¹Ethylene Ethylene Ethylene Ethylene Dipenta- Penta- Ethylene erythritolerythritol R² Ethylene Ethylene Ethylene Ethylene Ethylene EthyleneEthylene R³ Hexa- Hexa- Hexa- Tetra- Tolylene Xylylene Trimethylolmethylene methylene methylene methylene Propane- hexa- methylene R⁴Ethylene Ethylene Ethylene Propylene Propylene Ethylene Ethylene R⁵2-decyl 2-decyl 2-decyl 2-decyl 2-decyl 2-decyl 2-decyl Tetradecyltetradecyl tetradecyl tetradecyl tetradecyl tetradecyl tetradecyl h 1 11 1 1 1 2 m 2 2 2 2 6 4 2 k 125 67 250 125 35 50 67 n 20 10 20 20 10 20100

[0158] In addition to the aforementioned Preparation examples,commercially available hydrophobically modified polyether polyurethanecan also be used.

[0159] 1. Examples of the hair treatment agent composition

[0160] Examples and Comparative examples shown in the tables wereprepared with a conventional method. Using these samples, “tactilesensation at the time of application”, “tactile sensation of hair afterdrying (smoothness and ease of arranging the hair)”, and “temperaturestability (viroscosity)”were evaluated according to the followingevaluation methods.

[0161] Tactile sensation at the time of application

[0162] The sample was taken out of a container, an approximately 7 cmhigh plastic bottle with a one-touch cap on top, and used as a rinse;ease of application on the hair and comfortableness upon the applicationon the hair were evaluated by a panel of 20 specialists.

[0163] “Evaluation”

[0164] A: 18 or more panelists reported that ease of application orcomfortableness upon the application on the hair was good.

[0165] B: 14-17 panelists reported that ease of application orcomfortableness upon the application on the hair was good.

[0166] C: 8-13 panelists reported that ease of application orcomfortableness upon the application on the hair was good.

[0167] D: 7 or less panelists reported that ease of application orcomfortableness upon the application on the hair was good.

[0168] Tactile sensation of hair after drying (smoothness and ease ofarranging the hair)

[0169] After shampooing, 4 g of the prepared rinse was applied andrinsed away; after drying with a dryer, a panel of 20 specialistsevaluated smoothness and ease of arranging the hair.

[0170] “Evaluation”

[0171] A: 18 or more panelists reported that smoothness and ease ofarranging the hair were good.

[0172] B: 14-17 panelists reported that smoothness and ease of arrangingthe hair were good.

[0173] C: 8-13 panelists reported that smoothness and ease of arrangingthe hair were good.

[0174] D: 7 or less panelists reported that smoothness and ease ofarranging the hair were good.

[0175] Temperature stability (viscosity)

[0176] The prepared samples were put into 50-ml transparent glass tubesand stored in constant-temperature baths at 50° C., 37° C., 25° C., and0° C.; after six months, the samples' condition (viscosity) wasobserved. A cone/plate type or concentric cylinder type viscometer wasused for the viscosity mearurement, and the apparent viscosity at 25° C.and 1s⁻¹, and 100s⁻¹, was determined.

[0177] Evaluation was conducted as follows:

[0178] “Evaluation”

[0179] A: The change in the viscosity of each temperature sample was 10%or less compared with the initial viscosity (25° C.).

[0180] B: The change in the viscosity of each temperature sample was 20%or less compared with the initial viscosity (25° C.).

[0181] C: The change in the viscosity of each temperature sample was 30%or less compared with the initial viscosity (25° C.).

[0182] D: The change in the viscosity of each temperature sample wasmore than 30% compared with the initial viscosity (25° C.). TABLE 1-2“Examples 1-1 to 1-11: Rinse” Examples 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-81-9 1-10 1-11 Comparative example Stearyl 0.3 1.0 0.005 0.01 5 10 12trimethyl- ammonium chloride Behenyl 0.7 trimethyl- ammonium chlorideStearamido- 1.0 2.0 3.0 methyl dimethyl- amine Stearyl 5.0 5.0 alcoholPalmitic 0.6 2.0 5.0 5.0 0.02 0.04 20 40 48 acid Compound of 0.1 1.0 3.00.1 1.0 3.0 0.1 0.1 0.1 0.1 0.1 preparation example A of the presentinvention L-glutamic 0.01 0.2 0.6 0.9 1.8 0.2 0.2 0.2 0.2 0.2 acidPurified To 100 To 100 To 100 To 100 To 100 To 100 To 100 To 100 To 100To 100 To 100 water Tactile B A A A A B C B B B C sensation at the timeof application Tactile B A A A A B B B A A A sensation of the hair afterdrying Temperature B A A A A B B B A A A stability Viscosity (Pa · s)25° C. 1S⁻¹ 0.78 1.8 9.8 2.2 5.6 12.4 0.44 0.82 15.0 16.4 29.0 25° C.100S⁻¹ 0.10 0.12 0.37 0.15 0.30 0.44 0.10 0.11 0.48 0.77 1.0 Mole ratio*1:2.7 1:4.4 1:6.8 1:6.8 1:3.4 1:2.4 1:5.4 1:5.4 1:5.4 1:5.4 1:5.4

[0183] TABLE 1-3 “Comparative examples 1-1 to 1-6: Rinse” ExamplesComparative example 1-1 1-2 1-3 1-4 1-5 1-6 Stearyl 0.3 1.0 trimethyl-ammonium chloride Behenyl 0.7 trimethyl- ammonium chloride Stearamido-1.0 2.0 3.0 methyl dimethylamine Stearyl alcohol 5.0 5.0 Palmitic acid0.6 2.0 5.0 5.0 Compound of preparation example A of the presentinvention L-glutamic acid 0.01 0.2 0.6 0.9 1.8 Purified water to 100 to100 to 100 to 100 to 100 to 100 Tactile sensa- D D D C C D tion at thetime of application Tactile sensa- D D D C C C tion of the hair afterdrying Temperature D D D C C C stability Viscosity (Pa · s) 25° C. 1S⁻¹0.22 0.18 0.16 0.45 0.40 0.29 25° C. 100S⁻¹ 0.08 0.07 0.07 0.09 0.090.08 Mole ratio 1:2.7 1:4.4 1:6.8 1:6.8 1:3.4 1:2.4

[0184] TABLE 1-4 “Examples 1-12 to 1-14 and Comparative examples 1-7 to1-9: Conditioning shampoo” Examples 1-12 1-13 1-14 Comparative example1-7 1-8 1-9 Sodium 7.0 9.0 9.0 7.0 9.0 9.0 N-cocoyl-N- methyl taurateCocoyl amide 7.0 3.0 3.0 7.0 3.0 3.0 propyldimethyl glycine Stearyl 0.120.15 0.12 0.15 trimethyl- ammonium chloride Stearamido- 0.1 0.1 methyldimethylamine Stearyl alcohol 0.25 0.8 1.0 0.25 0.8 1.0 Palmitic acid0.1 0.1 Compound of 0.3 0.5 1.0 preparation example A of the presentinvention Purified water to 100 to 100 to 100 to 100 to 100 to 100Tactile sensa- A A A C C C tion at the time of application (shampoo)Tactile sensa- A A A D D D tion of the hair after drying Temperature A AA D D D stability Viscosity (Pa · s) 25° C. 1S⁻¹ 2.5 4.6 9.0 0.47 0.400.25 25° C. 100S⁻¹ 0.16 0.30 0.40 0.09 0.09 0.08 Mole ratio* 1:3.4 1:8.61:9.5 1:3.4 1:8.6 1:9.5

[0185] The aforementioned investigation indicated that the hairtreatment agent composition of the present invention is superior intactile sensation at the time of application, tactile sensation of thehair after drying, and temperature stability. TABLE 1-5 “Examples 1-15to 1-20: Rinse” Examples 1-15 1-16 1-17 1-18 1-19 1-20 Comparativeexample Stearyl 1.0 1.0 1.0 1.0 1.0 1.0 trimethyl- ammonium chlorideBehenyl trimethyl- ammonium chloride Stearamido- methyl dimethylamineStearyl alcohol 3.0 3.0 3.0 3.0 3.0 3.0 Palmitic acid 1.0 1.0 1.0 1.01.0 1.0 Compound of 0.05 0.1 1.0 5.0 10.0 15.0 preparation example A ofthe present invention L-glutamic acid 0.1 0.1 0.1 0.1 0.1 0.1 Purifiedwater to 100 to 100 to 100 to 100 to 100 to 100 Tactile sensa- B B A A BC tion at the time of application Tactile sensa- B B A A A B tion of thehair after drying Temperature C A A A A B stability Viscosity (Pa · s)25° C. 1S⁻¹ 0.72 0.98 1.6 7.0 12.3 29.0 25° C. 100S⁻¹ 0.10 0.11 0.120.35 0.44 1.1 Mole ratio* 1:5.2 1:5.2 1:5.2 1:5.2 1:5.2 1:5.2

[0186] The aforementioned investigation indicated that the desirableblend ratio of the hydrophobically modified polyether polyurethane to beblended in the composition of the present invention is 0.1-10 wt %.

[0187] Also, results shown in Table 1-2-1-5 indicate that, in order toobtain superior tactile sensation at the time of application, theviscosity should preferably be 1-10 Pa·s as measured at 25° C. and 1s⁻¹or 0.1-1 Pa·s as measured at 25° C. and 100s⁻¹. TABLE 1-6 “Examples 1-21and Comparative examples 1-10 to 1-12: Rinse” Examples 1-21 Comparativeexample 1-10 1-11 1-12 Stearyl trimethylammonium chloride Behenyltrimethylammonium 1.0 1.0 1.0 1.0 chloride Stearamidomethyl 0.1 0.1 0.10.1 dimethylamine Stearyl alcohol 3.0 3.0 3.0 3.0 Palmitic acid Compoundof preparation 1.0 example A of the present invention Carboxy vinylpolymer 1.0 Xanthan gum 1.0 PEG 11000 1.0 L-glutamic acid 0.1 0.1 0.10.1 Purified water to 100 to 100 to 100 to 100 Tactile sensation at theA C B D time of application Tactile sensation of the A D D C hair afterdrying Temperature stability A D C D Viscosity (Pa · s) 25° C. 1S⁻¹ 3.070.2 12.4 0.51 25° C. 100S⁻¹ 0.17 3.0 0.79 0.09 Mole ratio * 1:4 1:4 1:41:4

[0188] The aforementioned investigation indicated that the compositionof the present invention has superior characteristics compared with acomposition containing a commonly-used polymer thickener. TABLE 1-7“Examples 1-22 to 1-27: Rinse” Examples 1-22 1-23 1-24 1-25 1-26 1-27Comparative example Stearyl 0.1 0.1 0.2 0.1 0.1 trimethyl- ammoniumchloride Behenyl 0.2 0.2 trimethyl- ammonium chloride Cetyltrimethyl-0.1 0.1 ammonium chloride Stearamido- 0.2 0.2 0.1 0.1 methyldimethylamine Stearamido- 0.1 0.1 0.1 ethyl diethylamine Behenamido- 0.1propyl dimethylamine Cetyl alcohol 0.2 0.3 0.2 0.9 1 1.2 Stearyl alcohol0.2 0.3 0.5 0.6 0.7 0.9 Behenyl 0.2 0.3 0.5 0.6 0.5 0.6 alcohol Palmiticacid Stearic acid Myristic acid Oleic acid Isostearic acid 12-hydroxy-stearic acid Behenic acid Compound of 0.2 0.2 0.2 0.2 0.2 0.2preparation example A of the present invention L-glutamic acid Purifiedwater to 100 to 100 to 100 to 100 to 100 to 100 Tactile sensa- B B A A BC tion at the time of application Tactile sensa- C A A A A B tion of thehair after drying Temperature B B A A A B stability Viscosity (Pa · s)25° C. 1S⁻¹ 0.66 0.93 3.4 8.0 14.1 24.1 25° C. 100S⁻¹ 0.10 0.11 0.160.41 0.49 1.12 Mole ratio * 1:2 1:3 1:4 1:5 1:10 1:12

[0189] The aforementioned investigation shows that the molar ratio ofthe cation surfactant and the higher alcohol and/or higher fatty acid ispreferably 1:2-1:10 for the composition of the present invention. TABLE1-8 “Examples 1-28 to 1-33: Rinse” Examples 1-28 1-29 1-30 1-31 1-321-33 Comparative example Stearyl 0.1 0.1 0.1 0.1 0.1 0.1 trimethyl-ammonium chloride Behenyl trimethyl- ammonium chloride Cetyltrimethyl-ammonium chloride Stearamido- 0.1 0.1 0.1 0.1 0.1 0.1 methyldimethylamine Stearamido- 0.1 0.1 0.1 0.1 0.1 0.1 ethyl diethylamineBehenamido- propyl dimethylamine Cetyl alcohol Stearyl alcohol Behenylalcohol Palmitic acid 0.1 0.2 0.1 0.2 0.5 0.5 Stearic acid 0.2 0.2 0.40.8 0.8 0.8 Myristic acid 0.1 0.2 0.1 0.2 0.3 0.3 Oleic acid 0.1 0.2 0.20.3 Isostearic acid 0.1 0.2 0.2 0.3 12-hydroxy- 0.05 0.1 0.1 0.3 stearicacid Behenic acid 0.05 0.1 0.1 0.3 Compound of 0.2 0.2 0.2 0.2 0.2 0.2preparation example A of the present invention L-glutamic acid Purifiedwater to 100 to 100 to 100 to 100 to 100 to 100 Tactile sensa- B B A A BC tion at the time of application Tactile sensa- C A A A A B tion of thehair after drying Temperature B B A A A B stability Viscosity (Pa · s)25° C. 1S⁻¹ 0.76 0.81 3.6 7.6 15.3 22.2 25° C. 100S⁻¹ 0.11 0.11 0.140.34 0.50 1.2 Mole ratio * 1:2 1:3 1:4 1:5 1:10 1:12

[0190] The aforementioned investigation indicated that the compositionof the present invention has superior characteristics compared with acomposition containing a commonly-used polymer thickener.

[0191] The following test was conducted to verify the unexpected effectof the present invention.

[0192] “Effect of R⁵ on general formula (1)”

[0193] It was confirmed that the hydrophobic association of theassociative thickener of general formula (1) is enhanced by lengtheningof the chain of the end hydrophobic group and the system can bethickened more effectively.

[0194] A cone/plate type or concentric cylinder type viscometer was usedfor the viscosity mearurement, and the apparent viscosity at 25° C. and1s⁻¹, and 100s⁻¹, was determined. TABLE 1-9 R⁵ Viscosity of 1% Number ofsimple aqueous Viscosity of the carbon solution (Pa · s) rinse*² (Pa ·s) atoms*¹ 25° C. 1S⁻¹ 25° C. 100S⁻¹ 25° C. 1S⁻¹ 25° C. 100S⁻¹ 12 0.060.04 1.5 1.4 16 0.40 0.12 3.0 0.24 18 1.2 0.15 4.6 0.32 24 3.8 0.18 9.80.53

[0195] The compound having 24 carbon atoms is the hydrophobicallymodified polyether urethane of Preparation example A.

[0196] The compound having 18 carbon atoms was prepared by using EO20-mole adduct of stearyl alcohol for the compound corresponding togeneral formula (10) of Preparation example A.

[0197] The compound having 16 carbon atoms was prepared by using EO20-mole adduct of cetyl alcohol for the compound corresponding togeneral formula (10) of Preparation example A.

[0198] The compound having 16 carbon atoms was prepared by using EO20-mole adduct of lauryl alcohol for the compound corresponding togeneral formula (10) of Preparation example A. *²Rinse recipe Stearyltrimethylammonium chloride 2 wt % Stearyl alcohol 6 wt % Associativethickener shown in the table 1 wt % Ion-exchange water Balance

[0199] The aforementioned investigation shows that the thickening effectis enhanced not only in the simple aqueous solution but also in the hairtreatment agent composition of the present invention whenhydrophobically modified polyether urethane whose R¹ has 24 carbon atomswas used.

[0200] “Effect of blending organic acid”

[0201] It was verified that the addition of organic acid reduces colorloss of dyed hair, tightens cuticles and gives gloss to the hair.

[0202] The test was conducted by using a rinse prepared with thefollowing recipe. Stearyl trimethylammonium chloride 2 wt % Stearylalcohol 6 wt % Compound of preparation example A 1 wt % Organic acid(salt) shown in the table 0 or 0.5 wt %      Ion-exchange water Balance

[0203] TABLE 1-10 Citric Tartaric Glutamic Sodium Test item Not addedacid acid acid citrate Color loss 3.0 1.2 1.1 0.9 2.9 of dyed hair*¹Gloss of — ∘ ∘ ∘ x hair*²

[0204] Equation 1

[0205] Gloss=Mirror reflection of the maximum peak (S)±Maximum diffusionpeak in the direction of the normal line of the sample (D)

[0206] The gloss was determined with the above equation (S/D).

[0207] Those which had a gloss equivalent to or lower than that of “Notadded” were designated as “×”. Those which had a gloss higher than thatof “Not added” were designated as “◯”.

[0208] The aforementioned test shows that the addition of an organicacid suppresses color loss of dyed hair and increases the gloss of hair.

[0209] Additional Examples of the present invention are shown below. Inall of the following Examples, the hydrophobically modified polyetherurethane is a commercial product (Adecanol GT-700 from Asahi DenkaKogyo).

Example 1-34

[0210] Treatment hair pack Wt % Purified water Balance to make the totalof 100 weight parts Cetostearyl alcohol 7.00 Behenyl alcohol 5.00Dimethyl polysiloxane 1000cs 2.00 Cetyl isooctanoate 1.00Stearamidoethyl dimethylamine 3.00 DL-glutamic acid Amount needed toadjust the system pH to 4.2 Soy bean lecithin 0.10 Isoprene glycol 5.00Hydrophobically modified 0.50 polyether polyurethane Methylparaben 0.20Disodium edetate 0.01 Phenoxyethanol 0.20 Blending perfume 0.50

[0211] Purified water was heated up and the higher alcohol and other oilingredients were added, followed by vigorous stirring. Glutamic acid wasadded to the system to lower the pH and turn the system into anemulsion; other ingredients were added and, after stirring and mixing, ahigh efficiency disperser was used to adjust the particle size of theoil ingredients to 5 micrometers or less, followed by rapid cooling by aheat exchanger to obtain a treatment hair pack.

Example 1-35

[0212] Hair conditioner Wt % Purified water Balance to make the total of100 weight parts Cationic polymer (Nalco Chemical 1.00 Company; Merquat550) Cetostearyl alcohol 2.50 Behenyl alcohol 2.00 Partiallyamino-modified dimethyl 0.20 polysiloxane 50000cs Partiallypolyoxyethylene 0.20 modified dimethyl polysiloxane 100cs Dimethylpolysiloxane 20cs 1.80 Isononyl isononanoate 0.50 12-hydroxystearic acid0.50 Stearamidoethyl dimethylamine 0.80 DL-glutamic acid Amount neededto adjust the system pH to 4.2 Dipotassium glycyrrhizate 0.10 Isopreneglycol 3.00 Hydrophobically modified 0.50 polyether polyurethaneMethylparaben 0.20 Seaweed extract 0.10 Phenoxyethanol 0.20 Blendedperfume 0.50

[0213] Purified water was heated up and the higher alcohol and other oilingredients were added, followed by vigorous stirring. Silicones weremixed in a separate vessel and then added. Glutamic acid was added tothe system to lower the pH and turn the system into an emulsion; otheringredients were added and, after stirring and mixing, a high efficiencydisperser was used to adjust the particle size of the oil ingredients to3 micrometers or less, followed by rapid cooling by a heat exchanger toobtain a hair conditioner.

Example 1-36

[0214] Hair conditioner Wt % Purified water Balance to make the total of100 weight parts Cationic polymer (Nalco Chemical 1.00 Company; Merquat550) Cetostearyl alcohol 1.00 Behenyl alcohol 2.00 Polyoxyethylene (3)stearyl ether 0.20 Dimethyl polysiloxane 6cs 1.80 Isocetyl isostearate0.50 Stearyl trimethylammonium chloride 0.70 Succinic acid Amount neededto adjust the system pH to 4.2 Non-heat coagulated egg white 0.01Hydrogenated egg yolk oil 0.01 Vitamin E acetate 0.01 Soy bean extract0.10 Propylene glycol 10.00 Hydrophobically modified 0.50 polyetherpolyurethane Methylparaben 0.20 Phenoxyethanol 0.20 Blended perfume 0.50

[0215] Purified water was heated up and the higher alcohol and other oilingredients were added, followed by vigorous stirring. Succinic acid wasadded to the system to lower the pH and turn the system into anemulsion; other ingredients were added and, after stirring and mixing, ahigh efficiency disperser was used to adjust the particle size of theoil ingredients to 3 micrometers or less, followed by rapid cooling by aheat exchanger to obtain a hair conditioner.

[0216] 2. Examples of the cleaning agent composition

[0217] The following Examples and Comparative examples were preparedwith a conventional method. Using these samples, “temperature stability”(visocosity), “visco-elasticity” (sensory evaluation of the viscosity ofthe product), “foam formation”, “foam durability” and “refreshingsensation during cleaning” of the cleaning agent were evaluatedaccording to the following evaluation methods.

[0218] Temperature stability (viscosity)

[0219] The prepared samples were put into 50-ml transparent glass tubesand stored in constant-temperature baths at 50° C., 37° C., 25° C., and0° C.; after six months, the samples' condition (viscosity) wasobserved. A cone/plate type or concentric cylinder type viscometer wasused for the viscosity mearurement, and the apparent viscosity at 25° C.and 1s⁻¹, and 100s⁻¹ was determined. Evaluation was conducted asfollows:

[0220] “Evaluation”

[0221] ⊚: The change in the viscosity of each temperature sample was 10%or less compared with the initial viscosity (25° C.).

[0222] ◯: The change in the viscosity of each temperature sample was 20%or less compared with the initial viscosity (25° C.).

[0223] Δ: The change in the viscosity of each temperature sample wasmore than 20% compared with the initial viscosity (25° C.).

[0224] Visco-elasticity (sensory evaluation of the product viscosity)

[0225] Each sample was extracted from a 50-ml transparent glass tubeonto a hand and dripping from the hand and ease of spreading wereevaluated by a panel of 20 people. Evaluation was conducted based on thefollowing criteria:

[0226] “Evaluation”

[0227] ⊚: 15 or more of the 20 people judged that the applicability atthe time of cleaning was good (no dripping from the hand; good spreadingwhen applied).

[0228] ◯: 11-14 of the 20 people judged that the applicability at thetime of cleaning was good (no dripping from the hand; good spreadingwhen applied).

[0229] Δ: 10 or less of the 20 people judged that the applicability atthe time of cleaning was good (no dripping from the hand; good spreadingwhen applied).

[0230] Foam formation

[0231] 400 ml of 40° C. artificial hard water (70 ppm calcium carbonate)was put into a 2,500 ml cylindrical container equipped with a stirrer,and 4 g of the prepared sample was added to it; the foam volume wasmeasured immediately following stirring at 4,500 rpm for one minute.

[0232] “Evaluation”

[0233] ⊚: Good foaming (foam volume 1,200 ml or more)

[0234] ◯: Fair foaming (foam volume 800 ml or more)

[0235] Δ: Poor foaming (foam volume less than 800 ml)

[0236] Foam durability

[0237] The foam volume was measured five minutes after theaforementioned foam formation measurement, and the ratio with the foamformation immediately following stirring was determined.

[0238] The ratio was calculated as (foam volume after 5 minutes/foamvolume immediately following stirring).

[0239] “Evaluation”

[0240] ⊚: Good foam durability (ratio 0.8 or higher)

[0241] ◯: Fair foam durability (ratio 0.6 or more and less than 0.8)

[0242] Δ: Poor foam durability (ratio less than 0.6)

[0243] Refreshing sensation (sensory evaluation during rinsing and aftertowel-drying)

[0244] 3 g of each sample was used for face washing and the refreshingsensation during rinsing and after towel-drying was evaluated by a panelof 20 people. Evaluation was conducted based on the following criteria:

[0245] “Evaluation”

[0246] ⊚: 15 or more of the 20 people judged that there was a refreshingsensation during rinsing and after towel-drying.

[0247] ◯: 11-14 of the 20 people judged that there was a refreshingsensation during rinsing and after towel-drying.

[0248] Δ: 10 or less of the 20 people judged that there was a refreshingsensation during rinsing and after towel-drying. TABLE 2-2 Examples 2-12-2 2-3 2-4 Comparative example 2-1 2-2 2-3 2-4 Sodium cocoyl 10.0 — — —10.0 — — — methyl taurate Sodium cocoyl — 10.0 — — — 10.0 — — glutamatePotassium laurate — — 7.0 — — — 7.0 — Potassium — — 3.0 — — — 3.0 —myristate Sodium cocoyl — — — 10.0 — — — 10.0 isethionate Cocoyl amide —— — — — — — — propyldimethyl glycine Preservative Appro- Appro- Appro-Appro- Appro- Appro- Appro- Appro- priate priate priate priate priatepriate priate priate amount amount amount amount amount amount amountamount Perfume Appro- Appro- Appro- Appro- Appro- Appro- Appro- Appro-priate priate priate priate priate priate priate priate amount amountamount amount amount amount amount amount Hydrophobically 1.0 1.0 1.01.0 — — — — modified polyether polyurethane described in preparationexample (A) of the present invention Purified water to 100 to 100 to 100to 100 to 100 to 100 to 100 to 100 Temperature ⊚ ⊚ ⊚ ⊚ Δ Δ Δ Δ stability(viscosity) Visco- ⊚ ⊚ ⊚ ⊚ Δ Δ Δ Δ elasticity Foam formation ⊚ ⊚ ⊚ ⊚ ⊚ ∘⊚ ∘ Foam durability ⊚ ⊚ ⊚ ⊚ ∘ ∘ ∘ ∘ Refreshing ⊚ ⊚ ⊚ ⊚ ∘ ∘ ∘ ∘ sensationViscosity (Pa · s) 25° C. 1S⁻¹ 2.8 3.4 1.9 1.4 0.1 0.1 0.06 0.05 25° C.100S⁻¹ 0.3 0.3 0.2 0.1 0.08 0.08 0.05 0.05

[0249] The aforementioned investigation indicates that the cleaningagent composition of the present invention has superior temperaturestability, viscosity, foam formation, and foam durability. On the otherhand, it has been shown that when the hydrophobically modified polyetherurethane is not blended in, temperature stability and sensory evaluationresults of the viscosity in particular are inferior. TABLE 2-3 Examples2-5 2-6 Comparative example 2-5 2-6 2-7 2-8 Sodium cocoyl methyl 5.0 2.01.0 5.0 2.0 1.0 taurate Sodium cocoyl glutamate — — — — — — Potassiumlaurate — — — — — — Potassium myristate — — — — — — Sodium cocoyl — — —— — — isethionate Cocoyl amide 5.0 8.0 9.0 5.0 8.0 9.0 propyldimethylglycine Preservative Appro- Appro- Appro- Appro- Appro- Appro- priatepriate priate priate priate priate amount amount amount amount amountamount Perfume Appro- Appro- Appro- Appro- Appro- Appro- priate priatepriate priate priate priate amount amount amount amount amount amountHydrophobically modified 1.0 1.0 1.0 — — — polyether polyurethanedescribed in preparation example (A) of the present invention Purifiedwater to 100 to 100 to 100 to 100 to 100 to 100 Temperature stability ⊚⊚ ⊚ Δ Δ Δ (viscosity) Visco-elasticity ⊚ ∘ Δ Δ Δ Δ Foam formation ⊚ ∘ Δ∘ ∘ Δ Foam durability ⊚ ⊚ ⊚ Δ Δ Δ Refreshing sensation ⊚ ⊚ ∘ ∘ Δ ΔViscosity (Pa · s) 25° C. 1S⁻¹ 9.8 12.0 0.5 0.3 0.5 0.1 25° C. 100S⁻¹0.8 0.9 0.08 0.04 0.08 0.04

[0250] The above investigation shows that the cleaning agent compositionof the present invention exhibits superior characteristics. On the otherhand, it has been shown that the sensory evaluation of the viscosity andthe foam formation become particularly poor when the weight ratiobetween the anionic surfactant and the ampholytic surfactant is higherthan 2:8. TABLE 2-4 Examples 2-7 2-8 2-9 2-10 2-11 2-12 Comparativeexample Sodium cocoyl methyl 12.0 12.0 12.0 12.0 12.0 12.0 taurateSodium cocoyl glutamate — — — — — — Potassium laurate — — — — — —Potassium myristate — — — — — — Sodium cocoyl — — — — — — isethionateCocoyl amide 6.0 6.0 6.0 6.0 6.0 6.0 propyldimethyl glycine PreservativeAppro- Appro- Appro- Appro- Appro- Appro- priate priate priate priatepriate priate amount amount amount amount amount amount Perfume Appro-Appro- Appro- Appro- Appro- Appro- priate priate priate priate priatepriate amount amount amount amount amount amount Hydrophobicallymodified 0.05 0.1 1.0 5.0 10.0 12.0 polyether polyurethane described inpreparation example (A) of the present invention Purified water to 100to 100 to 100 to 100 to 100 to 100 Temperature stability ∘ ⊚ ⊚ ⊚ ⊚ ⊚(viscosity) Visco-elasticity ∘ ∘ ⊚ ⊚ ∘ Δ Foam formation ⊚ ⊚ ⊚ ⊚ ∘ ∘ Foamdurability ∘ ∘ ⊚ ⊚ ⊚ ⊚ Refreshing sensation ∘ ⊚ ⊚ ⊚ ⊚ ∘ Viscosity (Pa ·s) 25° C. 1S⁻¹ 0.6 1.0 209 10.0 19.3 29.4 25° C. 100S⁻¹ 0.1 0.2 0.3 0.50.8 1.1

[0251] The above investigation shows that the best blend ratio of thehydrophobically modified polyether urethane in the cleaning agentcomposition of the present invention is 0.1-10 wt %. TABLE 2-5 Examples2-13 2-14 2-15 2-16 2-17 Comparative example Sodium cocoyl methyl 2.04.0 16.0 30.0 40.0 taurate Sodium cocoyl glutamate 0.5 0.5 0.5 0.5 0.5Potassium laurate — — — — — Potassium myristate — — — — — Sodium cocoyl— — — — — isethionate Cocoyl amide 0.5 1.0 4.0 8.0 10.0 PreservativeAppro- Appro- Appro- Appro- Appro- priate priate priate priate priateamount amount amount amount amount Perfume Appro- Appro- Appro- Appro-Appro- priate priate priate priate priate amount amount amount amountamount Hydrophobically 1.0 1.0 1.0 1.0 1.0 modified polyetherpolyurethane described in preparation example (A) of the presentinvention Purified water to 100 to 100 to 100 to 100 to 100 Temperaturestability ∘ ⊚ ⊚ ⊚ ∘ (viscosity) Visco-elasticity Δ ∘ ⊚ ∘ Δ Foamformation ∘ ⊚ ⊚ ⊚ ∘ Foam durability ∘ ⊚ ⊚ ⊚ ⊚ Refreshing sensation ∘ ⊚ ⊚⊚ ∘ Viscosity (Pa · s) 25° C. 1S⁻¹ 0.5 0.8 8.5 15.5 34.0 25° C. 100S⁻¹0.08 0.1 0.6 0.8 1.3

[0252] The above investigation shows that the best blend ratio of thesurfactant in the cleaning agent composition of the present invention is5-40 wt %. TABLE 2-6 Examples Comparative example 2-18 2-9 2-10 2-11Sodium cocoyl methyl 10.0 10.0 10.0 10.0 taurate Sodium cocoyl — — — —glutamate Potassium laurate — — — — Potassium myristate — — — — Sodiumcocoyl — — — — isethionate Cocoyl amide 4.0 4.0 4.0 4.0 propyldimethylglycine Preservative Appro- Appro- Appro- Appro- priate priate priatepriate amount amount amount amount Perfume Appro- Appro- Appro- Appro-priate priate priate priate amount amount amount amount Hydrophobically1.0 — — — modified polyether polyurethane described in preparationexample (A) of the present invention Carboxy vinyl polymer — 1.0 — —Xanthan gum — — 1.0 — PEG10000 — — — 1.0 Purified water to 100 to 100 to100 to 100 Temperature stability ⊚ Δ Δ Δ (viscosity) Visco-elasticity ⊚◯ ◯ ◯ Foam formation ⊚ Δ Δ ◯ Foam durability ⊚ Δ Δ Δ Refreshingsensation ⊚ Δ Δ Δ Viscosity (Pa · s) 25° C. 1S⁻¹ 5.5 45.0 0.7 1.0 25° C.100S⁻¹ 0.8 1.0 0.1 0.1

[0253] The above investigation shows that blending hydrophobicallymodified polyether urethane in the cleaning agent composition of thepresent invention is significantly superior to blending in other polymerthickeners.

[0254] Also, the aforementioned Examples indicate that, in order toobtain high evaluation results for the visco-elasticity (sensoryevaluation of the viscosity), the viscosity should preferably be 1-10Pa·s as measured at 25° C. and 1s⁻¹ or 0.1-1 Pa·s as measured at 25° C.and 100s⁻¹.

[0255] Other Examples are shown below. Each of these examples is acleaning agent composition that has superior viscosity and is superiorin terms of foam formation as well as foam durability and feelsrefreshing without a slimy sensation after rinsing-off.

Example 2-19

[0256] Body cleaning agent Potassium cocoate 20 Myristyldimethylaminoacetic acid betaine 3 Hydrophobically modified polyether 2polyurethane described in preparation examples A-G of the presentinvention Glycerin 5 Taurine 2.0 Citric acid 0.5 Dodecane-1,2-diolacetate sodium salt 3 Hydroxypropylmethyl cellulose 0.3 PerfumeAppropriate amount Purified water Balance (total 100)

[0257] For preparation, the aforementioned ingredients were heated up to70° C. and dissolved, followed by cooling down to 30° C.

Example 2-20

[0258] Gel-like cleaning agent Triethanolamine cocoate 10 Myristyldimethylaminoacetic acid betaine 10 Hydrophobically modified polyetherpolyurethane 1 described in preparation examples A-G of the presentinvention Glycerin 5 Citric acid 0.5 Dodecane-1,2-diol acetate sodiumsalt 5 Perfume Appropriate amount Purified water Balance (total 100)

[0259] For preparation, the aforementioned ingredients were heated up to70° C. and dissolved, followed by cooling down to 30° C.

Example 2-21

[0260] Shampoo Sodium cocoyl acylmethyl taurate 10 Cocoyl amidepropyldimethyl glycine 5 Glycerin 1 Citric acid 1 Taurine 1.5Methyltaurine 0.5 Hydrophobically modified 0.5 polyether polyurethanedescribed in preparation examples A-G of the present inventionCationized cellulose 0.5 Perfume Appropriate amount Purified waterBalance (total 100)

[0261] For preparation, the aforementioned ingredients were heated up to80° C. and dissolved, followed by cooling down to 30° C.

Example 2-22

[0262] Rinse Sodium N-stearoyl-N-methyl taurate 2.0 Stearyl alcohol 8.5Glycerin 5.0 Citric acid  0.03 Hydrophobically modified polyetherpolyurethane 0.5 described in preparation examples A-G of the presentinvention Kathon CG (preservative, from Rohm & Haas) Appropriate amountPerfume Appropriate amount Purified water Balance (total 100)

Example 2-23

[0263] Cleansing foam Potassium cocoate 25 Sodium cocoyl N-methyltaurate 5 Polyethylene glycol 400 10 Glycerin 20 Stearic acid 3Dodecane-1,2-diol acetate sodium salt 3 Taurine 2 Hydrophobicallymodified polyether polyurethane 0.5 described in preparation examplesA-G of the present invention Perfume Appropriate amount Purified waterBalance (total 100)

[0264] For preparation, the aforementioned ingredients were heated up to80° C. and dissolved, followed by cooling down to 30° C.

Example 2-24

[0265] Body shampoo Potassium cocoate 5 Cocoyl amide propyldimethylglycine 2 Propylene glycol 10 Dodecane-1,2-diol acetate sodium salt 10sodium N-cocoyl-N-methyl taurate 5 Taurine 1 Hydrophobically modifiedpolyether, polyurethane 0.5 described in preparation examples A-G of thepresent invention Perfume Appropriate amount Purified water Balance(total 100)

[0266] For preparation, the aforementioned ingredients were heated up to80° C. and dissolved, followed by cooling down to 30° C.

[0267] The following test was conducted to verify the unexpected effectof the present invention.

[0268] “Effect of R⁵ on general formula (1)”

[0269] It was confirmed that the hydrophobic association of theassociative thickener of general formula (1) is enhanced by lengtheningof the chain of the end hydrophobic group and the system can bethickened more effectively.

[0270] A cone/plate type or concentric cylinder type viscometer was usedfor the viscosity mearurement, and the apparent viscosity at 25° C. and1s⁻¹, and 100s⁻¹, was determined. TABLE 2-7 R⁵ Viscosity of 1% Numbersimple aqueous Viscosity of of carbon solution (Pa · s) shampoo*² (Pa ·s) atoms*¹ 25° C. 1S⁻¹ 25° C. 100S⁻¹ 25° C. 1S⁻¹ 25° C. 100S⁻¹ 12 0.060.04 0.2 0.04 16 0.40 0.12 1.9 0.1 18 1.2 0.15 3.4 0.2 24 3.8 0.18 9.00.4

[0271] The compound having 24 carbon atoms is the hydrophobicallymodified polyether urethane of Preparation example A.

[0272] The compound having 18 carbon atoms was prepared by using EQ20-mole adduct of stearyl alcohol for the compound corresponding togeneral formula (10) of Preparation example A.

[0273] The compound having 16 carbon atoms was prepared by using EO20-mole adduct of cetyl alcohol for the compound corresponding togeneral formula (10) of Preparation example A.

[0274] The compound having 16 carbon atoms was prepared by using EO20-mole adduct of lauryl alcohol for the compound corresponding togeneral formula (10) of Preparation example A. *2: Shampoo recipe Sodiumcocoyl methyl taurate  10 wt % Cocoyl amide propyldimethyl glycine   6wt % Associative thickener shown in the table 0.5 wt % Cationized starch0.5 wt % Ion-exchange water Balance

[0275] The aforementioned investigation shows that the thickening effectis enhanced not only in the simple aqueous solution but also in the hairtreatment agent composition of the present invention whenhydrophobically modified polyether urethane whose R⁵ has 24 carbon atomsis used.

[0276] “The effect of the cationized starch”

[0277] A shampoo was prepared with the following recipe and the smoothsensation and sticky sensation during rinsing after using the shampoowere evaluated.

[0278] The testing was conducted using the shampoo prepared with thefollowing recipe. Sodium cocoyl N-methyl taurate  10 wt % Cocoyl amidepropyldimethyl glycine   6 wt % Compound of preparation example A of thepresent 0.5 wt % invention Cationized starch or catinonized celluloseAmount indicated below Ion-exchange water Balance

[0279] Evaluattion method

[0280] Evaluation used an absolute scale of seven steps (−3, −2, −1, 0,+1, +2, and +3).

[0281] −3 and +3 were evaluated as follows.

[0282] Smooth sensation; (not smooth at all: −3→very smooth: +3)

[0283] Sticky sensation; (very sticky: −3→not sticky at all: +3)

[0284] The average of a panel of 8 persons was determined and thejudgment was made based on the following:

[0285] ×: Below -1.5

[0286] Δ: -1.5 to below +0.5

[0287] ◯: +0.5 to below +1.5

[0288] ⊚: +1.5 or above TABLE 2-8 Smooth sensation Lack of Blend ratio(wt %) during rinsing stickiness Cationized starch 0 x ⊚ 0 1 Δ ⊚ 0 2 ∘ ⊚0 5 ∘ ⊚ 1 0 ⊚ ⊚ 1 5 ⊚ ⊚ Cationaized cellulose 0 5 ∘ Δ 1 0 ⊚ x

[0289] The above results show that use of a shampoo containingcationized starch results in smooth rinsing and gives good sensationwithout stickiness during use.

[0290] Other Examples of the present invention are shown below. In allof the following Examples, the hydrophobically modified polyetherurethane is a commercial product (Adecanol GT-700 from Asahi DenkaKogyo).

Example 2-25

[0291] Shampoo Wt % Purified water Balance to make the total of 100weight parts Cationaized cellulose (JR −400 from Union Carbide 0.50Corporation) Sodium N-cocoyl-N-methyl taurate 5.00 Ethylene glycoldistearate 2.00 Cocoyl monoethanol amide 0.60 Citric acid Amount needeto adjust pH to 5.3 Propylene glycol laurate 2.00 Hydrophobicallymodified polyether polyurethane 0.50 Sodium benzoate 0.30 Disodiumedetate 0.01 Phenoxyethanol 0.20 Blended perfume 0.60 Cocoyl amidepropyldimethyl glycine 4.00 Lauryl dimethylamino acetic acid betaine4.00

[0292] Cationized cellulose was hydrated with purified water at normaltemperatures and, after raising the temperature up to 80° C., otheringredients were added; after stirring and mixing, the temperature waslowered to obtain a shampoo.

Example 2-26

[0293] Shampoo Wt % Purified water Balance to make the total of 100weight parts Cationic polymer (Merquat 550 from Nalco Chemical 0.50Company) Polyoxyethylene (2) sodium lauryl ether sulfate 9.00Dipropylene glycol 3.00 Ethylene glycol distearate 2.00 Cocoylmonoethanol amide 2.50 Hydrophobically modified polyether polyurethane0.50 POP-POE block copolymer (Pluaronic L-64 from 0.50 Asahi DenkaKogyo) Preservative (Kathon CG) 0.05 Disodium edetate 0.01 Blendedperfume 0.60 L-glutamic acid Amount neede to adjust pH to 5.0 Cocoylamide propyldimethyl glycine 7.00 Silicon emulsion (BY22-005 from DowCorning Toray 1.00 Co., Ltd.)

[0294] The ingredients were added one after another to purifiedwater andstirred and mixed at 80° C., followed by cooling to obtain a shampoo.

Example 2-27

[0295] Shampoo Wt % Purified water Balance to make the total of 100weight parts Cationized starch 0.20 Polyoxyethylene (2) sodium laurylether sulfate 12.00 Propylene glycol 5.00 Cocoyl monoethanol amide 2.00Hydrophobically modified polyether polyurethane 0.50 Preservative(Kathon CG) 0.05 Disodium edetate 0.01 Blended perfume 0.60 Succinicacid Amount neede to adjust pH to 5.0 Cocoyl amide propyldimethylglycine 7.00

[0296] The ingredients were added one after another to purified waterand stirred andmixedat 80° C., followed by cooling to obtain a shampoo.

Example 2-28

[0297] Shampoo Wt % Purified water Balance to make the total of 100weight parts Cationaized cellulose (Catinal LC-100 from Toho 0.30Chemical Industry Co., Ltd.) Polyoxyethylene (2) sodium lauryl ethersulfate 18.00 Decagylcerin monooleate 1.00 Cocoyl monoethanol amide 2.00Hydrophobically modified polyether polyurethane 0.50 Preservative(Kathon CG) 0.05 Disodium edetate 0.01 Blended perfume 0.60 Lactic acidAmount needed to adjust pH to 5.0 Dipotassium glycyrrhizate 0.10 Taurine2.00 Sodium pyrrolidone carboxylate 0.10 Cocoyl amide propyldimethylglycine 5.00

[0298] The ingredients were added one after another to purified waterand stirred andmixed at 80° C., followed by cooling to obtain a shampoo.

Example 2-29

[0299] Hair manicure conditioner Wt % Purified water (1) 20.00 Dimethylpolysiloxane gum: imethyl polysiloxane 1.00 20 m Pa · s (20:80)Cetostearyl alcohol 9.00 Sodium N-stearoyl-N-methyl taurate 1.00 Benzylalcohol 5.00 Glycerin monooleate 1.00 Hydrophobically modified polyetherpolyurethane 0.50 Royal jelly extract 0.05 Disodium edetate 0.01 Blendedperfume 0.60 Citric acid Amount needed to adjust pH to 3.0 Alizurolpurple 0.08 Taurine 2.00 Purified water Balance to make the total of 100weight parts

[0300] The ingredients were added one after another to 20 parts ofpurified water and stirred and mixed at 80° C., followed by cooling; therest of the purified water at normal temperature was then added and thetemperature was lowered by means of a heat exchanger to obtain a hairmanicure conditioner (cleaning agent rinse).

Example 2-30

[0301] Shampoo Wt % Purified water Balance to make the total of 100weight parts Cationaized cellulose (JR-400 from Union 0.50 CarbideCorporation) Sodium N-cocoyl-N-methyl taurate 5.00 Ethylene glycoldistearate 2.00 Cocoyl monoethanol amide 0.60 Citric acid Amount neededto adjust pH to 5.3 Propylene glycol laurate 2.00 Hydrophobicallymodified polyether polyurethane 0.50 Sodium benzoate 0.30 Disodiumedetate 0.01 Phenoxyethanol 0.20 Blended perfume 0.60 Cocoyl amidepropyldimethyl glycine 4.00 Lauryl dimethylamino acetic acid betaine4.00

[0302] Cationized cellulose was hydrated with purified water at normaltemperatures and, after raising the temperature up to 80° C., otheringredients were added; after stirring and mixing, the temperature waslowered to obtain a shampoo.

Example 2-31

[0303] Shampoo Wt % Purified water Balance to make the total of 100weight parts Cationic polymer (Merquat 550 from Nalco 0.50 ChemicalCompany) Polyoxyethylene (2) sodium lauryl ether sulfate 9.00Dipropylene glycol 3.00 Ethylene glycol distearate 2.00 Cocoylmonoethanol amide 2.50 Hydrophobically modified polyether polyurethane0.50 POP-POE block copolymer (Pluaronic L-64 from 0.50 Asahi DenkaKogyo) Preservative (Kathon CG) 0.05 Disodium edetate 0.01 Blendedperfume 0.60 L-glutamic acid Amount needed to adjust pH to 5.0 Cocoylamide propyldimethyl glycine 7.00 Silicon emulsion (BY22-005 from DowCorning 1.00 Toray Co., Ltd.)

[0304] The ingredients were added one after another to purified waterand stirred and mixed at 80° C., followed by cooling to obtain ashampoo.

Example 2-32

[0305] Shampoo Wt % Purified water Balance to make the total of 100weight parts Cationized starch 0.20 Polyoxyethylene (2) sodium laurylethersulfate 12.00 Propylene glycol 5.00 Cocoyl monoethanol amide 2.00Hydrophobically modified polyether polyurethane 0.50 Preservative(Kathon CG) 0.05 Disodium edetate 0.01 Blended perfume 0.60 Succinicacid Amount needed to adjust pH to 5.0 Cocoyl amide propyldimethylglycine 7.00

[0306] The ingredients were added one after another to purified waterand stirred andmixed at 80° C., followed by cooling to obtain a shampoo.

Example 2-33

[0307] shampoo Wt % Purified water Balance to make the total of 100weight parts Cationaized cellulose (Catinal LC-100 from Toho 0.30Chemical Industry Co., Ltd. ) Polyoxyethylene (2) sodium lauryl ethersulfate 18.00 Monoolein acid deca glycerin 1.00 Cocoyl monoethanol amide2.00 Hydrophobically modified polyether polyurethane 0.50 Preservative(Kathon CG) 0.05 Disodium edetate 0.01 Blended perfume 0.60 Lactic acidAmount needed to adjust pH to 5.0 Dipotassium glycyrrhizate 0.10 Taurine2.00 Sodium pyrrolidone carboxylate 0.10 Cocoyl amide propyldimethylglycine 5.00

[0308] The ingredients were added one after another to purified waterand stirred andmixed at 80° C., followed by cooling to obtain a shampoo.

[0309] Industrial Applicability

[0310] The present invention provides a hair treatment agent compositionwhich has good temperature stability in terms of the viscosity, exhibitssuperior fluid flow characteristics, achieves smoothness and ease ofarranging the hair after drying, and gives a superior sensation duringuse.

[0311] The present invention can provide a cleaning agent compositionthat has superior viscosity and is superior in terms of foam formationas well as foam durability and feels refreshing without a slimysensation after rinsing-off.

1. A hair treatment agent characteristically comprising the followingingredients (A) and (B): (A) Hydrophobically modified polyether urethanerepresented by the following general formula (1):R¹—{(O—R²)_(k)—OCONH—R³[—NHCOO—(R⁴—O)_(n)—R⁵]_(h)}_(m)  (1) [In thisformula, R¹, R², and R⁴ denote hydrocarbon groups which can be identicalor different from each other; R³ denotes a hydrocarbon group that canhave a urethane bond; R⁵ denotes a straight chain, branched chain, orsecondary hydrocarbon group (having 24 or more, preferably 24, carbonatoms); m is the number 2 or greater; h is the number 1 or greater; andk and n are independent numbers in the range of 0-1,000.] (B) Cationicsurfactant
 2. The hair treatment agent composition of claim 1 wherein R²and/or R⁴ in general formula (1) for the hydrophobically modifiedpolyether urethane are alkylene groups having 2-4 carbon atoms orphenylethylene groups that can be identical or different from eachother.
 3. The hair treatment agent composition of claim 1 or 2 whereinR³ in general formula (1) for the hydrophobically modified polyetherurethane is a polyisocyanate residue represented by R³—(NCO)_(h+1). 4.The hair treatment agent composition of claim 3 wherein saidpolyisocyanate residue represented by R³—(NCO)_(h+1) is a polyisocyanateresidue obtained by a reaction between di- to octa- hydric polyol anddi- to tetra- hydric polyisocyanate.
 5. The hair treatment agentcomposition of claim 1, 2, 3, or 4 wherein R¹ in general formula (1) forthe hydrophobically modified polyether urethane is a polyol representedby R¹—(OH)_(m).
 6. The hair treatment agent composition of claim 1, 2,3, 4, or 5 wherein R⁵ in general formula (1) for the hydrophobicallymodified polyether urethane is a hydrocarbon group derived fromdecyltetradecyl alcohol.
 7. The hair treatment agent composition ofclaim 1, 2, 3, 4, 5, or 6 wherein the hydrophobically modified polyetherurethane represented by general formula (1) is a product of a reactionbetween one, two or more polyether polyols represented byR¹—[(O—R²)_(k)—OH]_(m), one, two or more polyisocyanates represented byR³—(NCO)_(h+1), and one, two or more polyether monoalcohols representedby HO—(R⁴—O)_(n)—R⁵.
 8. The hair treatment agent composition of claim 1,2, 3, 4, 5, 6, or 7 wherein the cationic surfactant is a quartenaryammonium salt represented by the following general formula (2) or anamidoamine type compound represented by the following general formula(3).

[In this formula, R3 denotes an alkyl group or hydroxyalkyl group having14-22 carbon atoms, R4 denotes a benzyl group, hydroxyalkyl group, oralkyl group having 1-3 carbon atoms, R5 and R6 denote alkyl groups orhydroxyalkyl groups independently represented by either R3 or R4, and Xdenotes a halogen atom or an alkylsulfuric group having 1-2 carbonatoms.] R7CONH—(CH₂)_(x)N(R8)₂  (3) [In this formula, R7CO— denotes ahigher fatty acid residue having 12-24 carbon atoms, R8 denotes an alkylgroup having 1-4 carbon atoms, and x is an integer 2-4.]
 9. The hairtreatment agent composition of claim 8 wherein said quartenary ammoniumsalt is one, two or more selected from a group consisting ofstearyltrimethyl ammonium chloride, cetyltrimethyl ammonium chloride,and behenyltrimethyl ammonium chloride.
 10. The hair treatmentcomposition of claim 8 wherein said amidoamine-type compound is one, twoor more selected from a group consisting of stearamidoethyldiethylamine, stearamidopropyl dimethylamine, and behenamidopropyldimethylamine.
 11. The hair treatment composition of claim 1, 2, 3, 4,5, 6, 7, 8, 9, or 10 which additionally comprises a higher alcoholand/or higher fatty acid.
 12. The hair treatment agent composition ofclaim 11 wherein said higher alcohol is one, two or more selected from agroup consisting of cetyl alcohol, stearyl alcohol, and behenyl alcohol.13. The hair treatment agent composition of claim 11 wherein said higherfatty acid is one, two or more selected from a group consisting ofstearic acid, palmitic acid, myristic acid, oleic acid, isostearic acid,12-hydroxystearic acid, or behenic acid.
 14. The hair treatment agentcomposition of claim 11, 12, or 13 wherein the molar ratio of the cationsurfactant and the higher alcohol and/or higher fatty acid is 1:2-1:10.15. The hair treatment agent composition of claim 1, 2, 3, 4, 5, 6, 7,8, 9, 10, 11, 12, 13, or 14 wherein the blend ratio of thehydrophobically modified polyether urethane of general formula (1) is 0.1-10 wt % of the total amount of the hair treatment agent composition.16. The hair treatment agent composition of claim 1, 2, 3, 4, 5, 6, 7,8, 9, 10, 11, 12, 13, 14, or 15 wherein the blend ratio of a cationicsurfactant is 0.01-10 wt % of the total amount of the hair treatmentagent composition.
 17. The hair treatment agent composition of claim 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16 wherein theviscosity of the hair treatment agent composition is 1-10 Pa·s whenmeasured at 25° C. and 1s⁻¹ and/or 0.1-1 Pa·s when measured at 25° C.and 100s⁻¹.
 18. The hair treatment agent composition of claim 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17 wherein said hairtreatment agent composition is a hair conditioning agent.
 19. The hairtreatment agent composition of claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, or 18 which additionally contains organic acid(preferably tartaric acid or glutamic acid).
 20. The hair treatmentagent composition of claim 19 wherein said organic acid is tartaric acidor glutamic acid.
 21. A cleaning agent characteristically comprising thefollowing ingredients (A) and (B): (A) Hydrophobically modifiedpolyether urethane represented by the following general formula (I):General formula (1)R¹—{(O—R²)_(k)—OCONH—R³[—NHCOO—(R⁴—O)_(n)'R⁵]_(h)}_(m)  (1) [In thisformula, R¹, R², and R⁴ denote hydrocarbon groups which can be identicalor different from each other; R³ denotes a hydrocarbon group that canhave a urethane bond; R⁵ denotes a straight chain, branched chain, orsecondary hydrocarbon group (having 24 or more, preferably 24, carbonatoms); m is the number 2 or greater; h is the number 1 or greater; andk and n are independent numbers in the range of 0-1,000.] (B) Anionicsurfactant and/or ampholytic surfactant.
 22. The cleaning agentcomposition of claim 21 wherein R² and/or R⁴ in general formula (1) forthe hydrophobically modified polyether urethane are alkylene groupshaving 2-4 carbon atoms or phenylethylene groups that can be identicalor different from each other.
 23. The cleaning agent composition ofclaim 21 or 22 wherein R³ in general formula (1) for the hydrophobicallymodified polyether urethane is a polyisocyanate residue represented byR³—(NCO)_(h+1).
 24. The cleaning agent composition of claim 23 whereinsaid polyisocyanate residue represented by R³—(NCO)_(h+1) is apolyisocyanate residue obtained by a reaction between di- to octa-hydric polyol and di- to tetra- hydric polyisocyanate.
 25. The cleaningagent composition of claim 21, 22, 23, or 24 wherein R¹ in generalformula (1) for the hydrophobically modified polyether urethane is apolyol represented by R¹—(OH)_(m).
 26. The cleaning agent composition ofclaim 21, 22, 23, 24, or 25 wherein R⁵ in general formula (1) for thehydrophobically modified polyether urethane is a hydrocarbon groupderived from decyltetradecyl alcohol.
 27. The cleaning agent compositionof claim 21, 22, 23, 24, 25, or 26 wherein the hydrophobically modifiedpolyether urethane represented by general formula (1) is a product of areaction between one, two or more polyether polyols represented byR¹—[(O—R²)_(k)—OH]_(m), one, two or more polyisocyanates represented byR³—(NCO)_(h+1), and one, two or more polyether monoalcohols representedby HO—(R⁴—O)_(n)—R⁵.
 28. The cleaning agent composition of claim 21, 22,23, 24, 25, 26, or 27 wherein the anionic surfactant is represented bythe following general formulas (4), (5), or (6), General formula (4)R1CO—A—(CH₂)_(n)SO₃M1  (4) (In this formula, R1CO— denotes a saturatedor unsaturated fatty acid residue having 10-22 carbon atoms on average;a denotes any of the structures containing electron donor atoms —O—,—NH—, and/or —N(CH₃)—; M1 denotes hydrogen, alkali metal, alkaline earthmetal, ammonium or organic amine; and n denotes an integer 1-3) Generalformula (5) R2CONH—C(b)H—COOM2  (5) (In this formula, R2CO— denotes asaturated or unsaturated fatty acid residue having 10-22 carbon atoms onaverage; b denotes a hydrogen atom, —CH₃, or —(CH₂)_(n)—COOM3; M2 and M3denote hydrogen, alkali metal, alkaline earth metal, ammonium or organicamine; and n denotes an integer 1-3) General formula (6) R3COO—M4  (6)(In this formula, R3COO— denotes a saturated or unsaturated fatty acidresidue having 10-22 carbon atoms on average; M4 denotes hydrogen,alkali metal, alkaline earth metal, ammonium or organic amine; and ndenotes an integer 1-3).
 29. The cleaning agent composition of claim 21,22, 23, 24, 25, 26, 27, or 28 wherein the anionic surfactant is one,two, or more chosen from a group consisting of N-acylmethyl taurate,N-acyl taurate, and N-acyl isethionate.
 30. The cleaning agentcomposition of claim 21, 22, 23, 24, 25, 26, 27, 28, or 29 wherein theampholytic surfactant is an acetic acid betaine type or imidazoline typeampholytic surfactant.
 31. The cleaning agent composition of claim 21,22, 23, 24, 25, 26, 27, 28, 29, or 30 wherein the weight ratio betweenthe anionic surfactant and the ampholytic surfactant is 10:0-2:8. 32.The cleaning agent composition of claim 21, 22, 23, 24, 25, 26, 27, 28,29, 30, or 31 wherein the blend ratio of the hydrophobically modifiedpolyether urethane of general formula (1) is
 0. 1-10 wt % of the totalamount of the cleaning agent composition.
 33. The cleaning agentcomposition of claim 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, or 32wherein the blend ratio of the anionic surfactant or the ampholyticsurfactant is 5-40 wt % of the total amount of the cleaning agentcomposition.